Tris-amino-s-triazines

ABSTRACT

Certain tris-amino-s-triazines, N,N-bis(bis-amino-s-triazinyl)-alkylamines, and 1,4-bis-(bis-amino-s-triazinyl)-piperazines are surface-treating agents and are useful in various surface-treating compositions, particularly floor waxes, shoe polishes and textile softeners.

United States Patent 9,1 8 Int. Cl. C0711 55/24, 87/40 US. C]. 260 -24756 Claims ABSTRACT OF THE DISCLOSURE New tris-amino-s-triazines in which1 or 2 of the amino groups are heterocyclic rings are useful as surfacetreating agents. Compositions containing certain of these new triaziensand certain N,N-bis-(bis-amino-s-triazinyl)- alkylamines and 1,4 bis(bis-amino-s-triazinyl)piperazines are also useful for surface treating,particularly as floor waxes and shoe polishes, and as textile softeningcompounds.

CROSS-REFERENCE This application is a continuation-in-part of our parentapplication Ser. No. 560,855, filed June 27, 1966, now abandoned.

DETAILED DISCLOSURE This invention concerns new tris-amino-s-triazinesin which 1 or 2 of the amino groups are heterocyclic ring structuressuch as pyrrolidino, 4(lower alkyl)-piperazino, piperidino, morpholino,or hexamethyleneirnino. These compounds are useful as surface treatingagents and are the principal components of new surface treatingcompositions, such as floor wax. Certain of these compounds also findutility as textile softening agents.

By surface treating agents in the present description are meant agentswhich can be used for the protection and conservation, e.g. by coatingor waxing, of surfaces of all types such as, for example, agents for thetreatment of surfaces of inorganic materials such as metal, stone, tile,etc., and of organic materials such as wood, leather, synthetic plastics(e.g. linoleum), textiles, paper, etc.

More particularly, the surface treating agents according to thisinvention comprise, as principal constituent, s-triazine derivatives ofthe formula A represents the group in which R represents a lower alkylradical, namely an alkyl radical of from 1 to 5 carbon atoms, and Rrepre- 3,526,622 Patented Sept. 1, 1970 sents an alkyl radical havingfrom 10 to 18 carbon atoms,

B represents the group in which R, and R have the meanings given above,the pyrrolidino, piperidino, 4-lower alkyl-piperazino, morpholino orhexamethyleneimino group, and

C represents the pyrrolidino, piperidino, 4-methylenepiperazino,morpholino or hexamethyleneimino radical, or the grouping of the formulaBINIB Y I wherein each B has the meaning given above, and X is analkylimino radical or the piperazine-1,4-diyl radical, and, in thosecompounds falling under Formula I in which each of A and B representsthe group C represents besides the substituents defined above, also thegroup wherein each of R and R independently of the other represents asubstituted or unsubstituted alkyl radical having from 1 to 20 carbonatoms.

More in particular, the alkyl radicals symbolized by R and R, can besubstituted by halogen atoms such as fluorine, chlorine, or bromineatoms, or by hydroxyl groups. Preferably such substituted alkyl radicalshave not more than 5 carbon atoms. The alkyl radicals of the alkylaminogroup symbolized by X contains preferably from 1 to 5 carbon atoms.

The following classes of s-triazines are particularly valuable as maincomponents in the surface treating agents according to this invention.

(I) Compounds of the formula Af Tlq-Bl wherein A has the same meaning asin Formula I, B represents pyrrolidino, morpholino, piperidino, N-(loweralkyl)-piperazino or hexamethyleneimino, and C represents the samesubstituents as A, or as B or it represents the grouping in which eachof R and R represents lower alkyl, preferably of from 2 to 5 carbonatoms, susbtituted by hydroxyl, chlorine, bromine or fluorine; in thelatter case, C represents also a trifluoromethyl amino group.

The compounds of Formula IH in which C represents A or B are readilyemulsifiable.

(II) Compounds of the formula III, and R represents alkyl of from 1 to 5carbon atoms.

(III) Compounds of the formula Bi V) in which A and C have the samemeanings as in Formula III.

Among the compounds falling under Formulas III and IV, a subclass ofcompounds which fall under the formulas N chloro-lower alkyl Nhydroxy-lower alkyl and (VIII) wherein A and R have the same meanings asgiven hereinbefore, are textile softening agents which impart relativelylittle or no water repellance to detergent-hardened textile materialssoftened therewith, e.g. to towels and the like goods in whichwater-repellency is not desirable. The compounds are preferably appliedfrom alcoholic, e.g. from isopropanol solution. Application from glacialacetic acid solution is also possible but less desirable in view ofsmell and acidity of such agents, even after dilution with water.

On the other hand, a preferred class of compounds according to theinvention, which falls under the formulas wherein A and B have the samemeaning as given hereinbefore, and

wherein A has the same meaning as given hereinbefore, and C represents Aor B are distinguished as gloss-imparting, self-polishing Waxes whichare particularly useful as a principal constituent of dry-brightpolishing compositions.

Agents containing e.g. about 5% of the compounds of Formula X, whenused, e.g. as floor polishes, also have a distinct anti-slip effect;floors treated with such agents are much less slippery than thosetreated with floor polishes not containing a compound of Formula X.

Finally, compounds of a preferred subclass of the formula NNN wherein Aand R have the same meanings as given hereinbefore, are waxes of brownor dark-brown to brownish black shade and serve as polishing agents orprincipal constituents of such agents for polishing leather, e.g. shoeleather, especially also in order to retard the tendency of such leatherto absorb water.

The waxes of the Formulas IX to XI, inclusive, given hereinbefore arereadily emulsifiable. When used in major amounts (e.g. 20 to 70% byweight calculated on the total weight of solids) in surface-treatingagents, especially in floor polishes, they impart to such polishes acertain gloss which is further enhanced by rubbing, e.g. with a softcloth or the like, or, especially in the case of compounds of FormulaIX, in which B represents N-(lower alkyl)-piperazino, and in the case ofthe compounds of Formula X, supra, by subsequent washing of suchsurface, in particular floors, with water or with alkaline detergents.This consitutes an important progress, because many commerciallyavailable floor polishes will show enhanced gloss after rubbing with,e.g. a soft cloth or :1

polishing brush, but will not withstand washing with water andespecially not with alkaline agents.

In the compounds of Formula I, and especially in those of Formulas III,IV and V, the presence of at least one amino group having one shorterand one longer alkyl substituent as represented by A in those formulas,is necessary to obtain compounds suitable for use as main polishconstituent in surface treating agents according to the invention.

The trisamino-s-triazine derivatives of Formula I have well definedmelting points and wax-like properties; they can thus be used instead ofcommercial natural and synthetic waxes or together therewith for thetreatment and finishing of surfaces of all types. They have thecharacteristic properties of natural waxes such as solubility in fattysolvents, miscibility with natural and synthetic waxes and, with theaddition of suitable emulsifying agents, can be worked up in water toform finely dispersed emulsions. The new compounds produce coatingswhich are resistant to chemicals, particularly they have good stabilityto alkali. In their excellent suitability as waxes, they are equivalentfor all practical purposes to the montanic acid esters.

Surface-treating agents according to the invention are obtained bymixing a trisamino-s-triazine derivative of Formula I or several suchderivatives with the usual substances which are suitable for thetreatment of surfaces. Such substances are, for example, the following:natural and synthetic waxes, resins, silicones, etc. which improve thephysical properties, also solvents, as well as inorganic and organicfiller, e.g. silicates, milled plastics, anionic, cationic or non-ionicdispersing agents, cleansing agents such as, e.g. natural and syntheticsoaps, tensioactive substances, pigments, agents to improve thestability to light, stabilizers of all types such as corrosioninhibitors, scents, dyestuffs, biocidal active substances or agentscontaining such substances, e.g. insecticides, fungicides, bactericides,etc.

More particularly, the surface-treating agents accord ing to theinvention, for instance in the form of floor polishes, can also contain,besides a compound or compounds of Formula I, as main component,volatile solvents such as are used in wood-sealing agents, namely, ethylacetate, acetone, methylethyl ketone, ethanol, toluene and the like.

The surface-treating agents according to the invention can be in theform of and used as aerosols, solvents, emulsions, semi-solid and solidpastes. The agents can thus serve to protect and to finish surfaces(e.g. polishing waxes) of all types, by which is also included thetreatment of paper, e.g. the production of carbon paper.

Trisamino-s-triazines of Formula I wherein two bisamino-s-triazineradicals are bound together by the piperazine-l,4-diyl radical are knowncompounds. They can be obtained by reacting two molecules of a2-halogen-4,6-bis-amino's triazine correspondingly substituted in theamino group with piperazine, the reaction being performed attemperatures between 100 and 200 0, preferably in an inert gasatmosphere and optionally in the presence of an inert solvent and aproton acceptor.

The new trisamino-s-triazines of the more restricted general formula U(XII) wherein A and B have the meanings given in Formula I, and Crepresents the pyrrolidino, piperidino, 4-methylpiperazino, morpholinoor hexamethyleneimino radical or the group of the general formulawherein each of R and R have the meanings given in Formula I, areobtained according to the invention by reacting cyanuric chloride with(a) two mols of the same or with one mole of each of two differentsecondary amines containing the radicals R and R defined above and withone mol of a secondary amine containing the radicals R and R definedabove, or

(b) with two mols of the same or one mol of each of two differentsecondary amines containing the radicals R and R defined above and withone mol of pyrrolidine, piperidine, 4-methylpiperazine, morpholine orhexamethyleneimine, or

(c) with one mol of a secondary amine containing the radicals R and Rdefined above and with 2 mols of pyrrolidine, piperidine,4-methylpiperazine, morpholine or hexamethyleneimine or with one mol ofeach of two of the heterocyclic bases mentioned above, or

(d) with one mol of a secondary amine containing the radicals R and Rdefined above, one mol of pyrrolidine, piperidine, 4-methyl-piperazine,morpholine or hexamethyleneimine and with one mol of a secondary amineintroducing the group of general Formula XIII defined above, or

(e) with 2 mols of the same or one mol of each of two differentsecondary amines containing the radicals R and R defined above and withone mol of a secondary amine introducing the group of general FormulaXIII defined above,

the reaction optionally being performed in the presence of a solvent ordiluent and also a proton acceptor.

As solvent for the reaction of the first and second chlorine atom ofcyanuric chloride, those usual for this reaction are used such as water,mixtures of acetone and water, other mixtures of organic solvents withwater, halogen hydrocarbons and aromatic hydrocarbons. Inorganic basessuch as the carbonates and hydroxides of alkali metals, and organicbases such as secondary and tertiary amines are used as protonacceptors. The reaction temperature for the exchange of the firstchlorine atom is from -20 to +10 C., for the second chlorine atom from10 to and for the third chlorine atom from 100 to 200 C.

The following non-limitative examples describe surface finishing agentsaccording to the invention. Where not otherwise stated, parts andpercentages are given therein by weight. The abbreviations A.N. and S.N.signify acid number and saponification number, respectively. Thetemperatures are given in degrees centigrade.

EXAMPLE 1 4.95 parts of1,4-bis-[2',4-bis-N-methyl-N-n-octadecylamino-s-triazinyl- (6)]-piperazine, 4.05 parts of petroleum wax (M.P. 8688; A.N. 13-l6;

S.N. 45-55; penetration 4-6 at 100 g./25/5 sec.), 0.63 part of thecondensation product of oleyl alcohol and ethylene oxide (molar ratioabout 1:5), as emulsifier, 0.54 part of olein, 0.54 part of aminomethylpropanol, 77.89 parts of water.

1.20 parts of colophoniurn-modified phenolic resin having a meltingpoint of about 152, the phenolic resin base of which is produced asdescribed in Example 2 of US. Pat. 2,532,374,

0.40 part of cone. ammonia,

8.40 parts of water.

0.02 part of trimethyl-('y-perfiuoro-octylamido-propylene)-ammoniumiodide, as wetting agent,

0.40 part of tris-(butoxyethyl)-phosphate,

0.98 part of water.

The components of the mixture (a), with the exception of water, aremelted at 150, the homogeneous melt is cooled to 100-110" and thenslowly added, while stirring strongly, to the boiling water. Theemulsion formed is cooled to room temperature and first the mixture (b)and then mixture (c) are added while stirring.

The resultant gloss-imparting emulsion Wax composition is excellentlysuitable for the care of modern floors, polyvinyl chloride tiles beinggiven a polish value of 27.7 measured on a 45 glossmeter of the Langetype (100 being the gloss of a black mirror viewed under an angle of 45As a comparison an emulsion produced according to the above example inwhich the abovementioned piperazine derivative according to theinvention was replaced by carnauba wax only attained a polish value of17.7. In addition, the wax emulsion produced according to the aboveexample with the substance according to the invention is considerablyless slippery than one produced with carnauba wax.

The s-triazine derivative which is a main component of theabove-described surface-treating composition, is of the structuralformula CH3 N N /CH8 r ra -r n 0151121 N L N L; 1s a1 1 CH3 31131 Cfia0131137 and is produced as follows 37 parts of2,4,6-trichloro-s-triazine are dissolved in 400 parts of anhydroustoluene and, at room temperature, a solution of 120 parts ofN,N-dimethyl-N-n-octadecylamine in 400 parts of anhydrous toluene isadded dropwise. The whole is then refluxed under an atmosphere ofnitrogen until the calculated amount of chloromethane has been splitoff. The solvent is then distilled off in vacuo. After recrystallizationfrom acetone, the 2-chloro-4,6-bis-N-methy1-N-n-octadecylamino-striazine melts at 58-62.

34 parts of 2-chloro-4, 6-bis-N-methyl-Nn-octadecylamino-s-triazine and10 parts of piperazine are heated for 5 hours at 110-115 under anatmosphere of nitrogen. After cooling, excess piperazine and piperazinehydrochloride which have been formed are removed by washing with waterand the residue is dried. 1,4-bis-[2',4- bis Nmethyl-N-n-octadecyl-amino-s-triazinyl-(6')]- piperazine is obtained.After recrystallization from dioxan it melts at 98-102.

EXAMPLE 2 2.24 parts of1,4-bis-[2-morpholino-4-methyl-N-n-octadecylamino-s-triazinyl- 6')]-piperazine,

1.68 parts of carnauba wax,

1.68 parts of ester wax (montanic acid ester, M.P. 80-

83"; A.N. 20-30; S.N. 135-150),

0.44 part of the same emulsifier as used in Example 1,

040 part of olein,

0.40 part of aminomethyl propanol,

33.16 parts of water.

16.70 parts of an aqueous dispersion of polystyrene (emulsion polymer)having a solids content of about 36% by Weight,

0.10 part of the condensation product of nonylphenol and ethylene oxide(molar ratio about 1:15), 23.20 parts of water.

3.00 parts of alkali-soluble pentaerythritol resinate polyester resinhaving a melting range of 169-181 and an acid number of 190-200, aslevelling agent,

1.00 part of cone. ammonia,

16.00 parts of water.

The components of the mixture (a), with the exception of the water, aremelted at 150, the homogeneous melt is cooled to 100-110" and thenadded, while stirring strongly, to the boiling Water. The emulsionformed is cooled to room temperature and the mixtures (b) and (c) areadded one after the other while stirring.

The resultant dry-bright wax-polymer emulsion is excellently suited forthe care of modern floors in that the coating itself possess a certaingloss which can, however, be increased by polishing to a value of 24.3.

The s-triazine derivative, which is used as a main component in theabove-described surface-treating composition, is produced as follows.

185 parts of cyanuric chloride are dissolved in 1000 parts of carbontetrachloride and 87.1 parts of morpholine are added while stirringintensively at 0 to 5'. A solution of 54 parts of sodium carbonate in300 parts of water is then added. After stirring for 2 hours, a solutionof 290 parts of N-methyl-N-n-octadecylamine in 1000 parts of carbontetrachloride is added dropwise at 10 to 15 and then a solution of 54parts of sodium carbonate in 300 parts of water is added dropwise. TheWhole is then slowly heated and afterwards refluxed for 5 hours. Oncompletion of the reaction, the solvent is distilled oflf. The residueis stirred with 1500 parts of acetone. The undissolved part is filteredoff under suction, thoroughly washed with water and dried.2-chloro-4-morpholino-6- N-methyl N n octadecylamino-s-triazine isobtained which, after recrystallization from alcohol, melts at 52-54.

482 parts of 2-chloro-4-morpholino-G-N-methyl-N-noctadecylamino-s-triazine and 100 parts of piperazine are dissolved in4000 parts of warm xylene and 45 parts of pulverized sodium hydroxideare added. The whole is then refluxed using a water separator under anatmosphere of nitrogen. On completion of the water separation, themixture is refluxed for another 3 hours. The reaction mixture isfiltered hot, the filtrate is evaporated to dryness in vacuo and theresidue is stirred with 4000 parts of acetone. The solid, undissolvedpart is separated, thoroughly washed with water and dried in vacuo. 1,4-bis-[2'-morpholino 4 N methyl-N-n-octadecylaminos-triazinyl-(6)]-piperazine is obtained which, after recrystallizationfrom acetic acid ethyl ester, melts at 108-112".

EXAMPLE 3 4.250 parts of N,N-bis- [2'-N'-methyl N noctadecylamino-4'-morpholino-s-triazinyl-(6'-)]-N ethylamine,

4.250 parts of wax (montanic acid ester, M.P. '-83;

A.N. 20-30; S.N. 135-150),

4.250 parts of petroleum wax (M.P. 86-88"; A.N. 13-16;

S.N. 45-55; penetration 4-6 at g./25/ 5 sec.),

0.850 part of olein,

0.765 part of the same emulsifier as in Example 1,

0.680 part of aminornethyl propanol,

69.955 parts of water.

2.250 parts of the same colophonium-modified phenolic resin as used inExample 1,

0.675 part of cone. ammonia,

12.075 parts of water.

The components of the mixture (a), with the exception of the Water, aremelted at 150, the homogeneous melt is cooled to 100-110 and then slowlyadded, while stirring, to the boiling water. The emulsion formed iscooled to room temperature and the mixture (b) is added while stirring.

The resultant dry-bright emulsion wax is excellently suitable for thecare of modern floors; it is self-polishing, but its gloss can still beincreased by subsequent rubbing with a soft cloth. If this coatingobtained on polyvinyl chloride tiles is washed with a moist cloth thenthe gloss value rises from 29 to 35 whilst, as a comparison, the glossvalue of an emulsion produced according to the above example in whichthe wax body according to the invention is replaced by carnauba wax onlyrises on washing from 29.5 to 30.5.

A similar composition is obtained when replacing the triazinyl componentin the above composition by an equivalent amount of2-morpholino-4,6-bis-(N-methyl-N- n-octadecyl-amino)-s-triazine or ofN,N-bis-[2,4-di-(N'- methyl-N'-n-octadecylamino)-s-triazinyl-(6)] Nethylamine.

The s-triazine derivatives used in the above compositions are producedas follows:

(1) 48.2 parts of6-chloro-2-(N-methyl-N-n-octadecylamino)-4-morpholino-s-triazine and49.2 parts of 6-ethylamino-2-N-rnethyl-N-n-octadecylamino 4morpholino-striazine are dissolved by heating in 400 parts by volume ofanhydrous pyridine while stirring. The reaction mixture is then refluxedfor 18 hours under an atmosphere of nitrogen whereupon it is filteredhot, the filtrate is concentrated to dryness in vacuo and the residuethoroughly washed with water and dried in vacuo. N,N-bis-[2,N'-methyl-N-n-octadecylamino 4' morpholino-s-triazinyl- (6)]-N-ethyl-amineis obtained which, after recrystallization from acetone, melts at 76-78.

(2) 37 parts of cyanun'c chloride are dissolved in 400 parts ofanhydrous toluene and, at room temperature, a solution of 120 parts ofN,N-dimethyl-N-n-octadecylamine in 400 parts of anhydrous toluene isadded dropwise. The whole is then refluxed under an atmosphere ofnitrogen until the calculated amount of chloromethane has been splitoff. The solvent is then distilled oif in vacuo. After recrystallizationfrom acetone, the 2-chloro-4,6-bisN-methyl-N-n-octadecylamino-s-triazine melts at 58-62.

34 parts of 2-chloro-4,6-bis-N-methyl-N-n-octadecylamino-s-triazine and10 parts of morpholine are heated for 5 hours at 110-115 under anatmosphere of nitrogen. After cooling, excess morpholine and morpholinehydrochloride which have been formed are removed by washing with waterand the residue is dried. 2-morpholino-4,6- bis-(N-methyl-N noctadecylamino) s triazine is obtained, which after recrystallizationfrom methyl alcohol melts at 8082.

(3) 67.8 parts of2-chloro-4,6-bis-N-methyl-N-n'octadecyl-amino-s-triazine and 68.7 partsof 2-ethylamino-4,6- bis-N-methyl-N-n-octadecylamino-s-triazine aredissolved by heating in 400 parts by volume of anhydrous pyridine whilestirring. The reaction mixture is then refluxed for 18 hours under anatmosphere of nitrogen whereupon it is filtered hot, the filtrate isconcentrated to dryness in vacuo and the residue thoroughly washed withwater and dried in vacuo.N,N-bis-[2,4-di-(N-methyl-N-n-octadecylamino)-s-triazin-(6)-yl] Nethylamine is obtained which, after recrystallization from acetone,melts at 5557. When this brownish-black substance is incorporated in asurface-treating agent of the composition given in Example 3, in lieu ofthe tri-substituted ethylamine component, and black boot leather ispolished therewith, it is given a black gloss similar to that of astandard black boot polish, and a retarded tendency to absorb water.

EXAMPLE 4 5.0 parts of 2-(N'-methyl-piperazino)-4-morpholino6-(N-methyl-N"-n-octadecylamino) s triazine are dissolved in 95.0 partsof isopropanol, if necessary while heatiang, whereupon a clear solutionis formed. This solution is excellently suitable for softening textilesparticularly cotton towelling which has become hardened by repeatedwashing. Such goods are laid for a few minutes in a bath which contains40 parts of the above-mentioned solution per 1000 parts by volume ofWater. After treatment in this bath, the goods are wrung out and driedin the air. Even greatly hardened and scratchy cotton towelling regainsits original soft and fleecy handle. It is not rendered unduly waterrepellant by such treatment.

Similar good softener dispersions are produced as described in Example4, supra, by replacing the 40 parts of isopropanolic 5%-softenersolution used therein by the same amount of an isopropanolic 5%-solutionof N .N- bis-[2,4-di-(N'-methyl-N'-n-octadecyl-amino) striazinyl-(6)]-N-ethylamine, or by 4 parts of an isopropanolic 5-solution of 2,4-di- (N-methyl-N-n-octadecyl-amino6-[N-(B-hydroxyethyl)-N-(/3-chloroethyl)-amino]-s triazine. M.P. -82".

The textile softener compound used in Example 4, supra, is produced asfollows:

185 parts of cyanuric chloride are dissolved in 1000 parts of carbontetrachloride and 87.1 parts of morpholine are added while stirringintensively at 0 to 5. A solution of 54 parts of sodium carbonate in 300parts of Water is then added. After stirring for 2 hours, a solution of290 parts of N-methyl-N-n-octadecylamine in 1000 parts of carbontetrachloride is added dropwise at 10 to 15 and then a solution of 54parts of sodium carbonate in 300 parts of Water is added dropwise. Thewhole is then slowly heated and afterwards refluxed for 5 hours. Oncompletion of the reaction, the solvent is distilled off. The

residue is stirred with 1500 parts of acetone. The undissolved part isfiltered off under suction, thoroughly washed with water and dried.2-chloro-4-morpholino-6-N-methyl- N-n-octadecylamino-s-triazine isobtained which, after recrystallization from alcohol, melts at 5 2-54".

482 parts of2-chloro-4-morpholino-G-N-methyl-N-noctadecylamino-s-triazine and partsof N-methylpiperazine are dissolved in 4000 parts of Warm xylene and 45parts of pulverized sodium hydroxide are added. The Whole is thenrefluxed in a water separator under an atmosphere of nitrogen. Oncompletion of the water separation, the mixture is refluxed for another3 hours. The reaction mixture is filtered hot, the filtrate isevaporated to dryness in vacuo and the residue is stirred with 4000parts of acetone. The solid, undissolved part is separated, thoroughlywashed with water and dried in vacuo. 2-N- methylpiperazino-4-morpholino6-N"-methyl-N-n-octadecylamino-s-triazine is obtained which, afterrecrystallisation from dioxan melts at 48-51 EXAMPLE 5.DRY-BRIGHTEMULSION WAX 3.19 parts of 2,4-bis-(N-methyl-N-n-octadecyl-amino)-6-(N'-methyl-piperazino)-s-triazine,

3.19 parts of paraffin (M.P. 50-52 )1,

6.38 parts of montanic acid ester Wax (M.P. 80-83 A.N.

1.70 parts of olein,

1.36 parts of aminomethyl propanol,

1.53 parts of cetyl alcohol polyglycol ether with 4 to 5 ethyleneoxygroups, as emulsifying agent,

67.66 parts of water.

2.25 parts of the same colophonium-modified phenolic resin as used inExample 1,

0.67 part of aqueous concentrated ammonia (25%), and

12.07 parts of water.

The components of mixture (a), with the exception of the water, aremelted at and stirred until a homogeneous melt is obtained. The melt iscooled to 100110,

1 1 the water is brought to the boil and is then added thereto, and theresulting mixture (a) is cooled to room temperature. This mixture (a) isobtained in the form of an emulsion to which the solution (b) is added.The resultant emulsion is excellently suitable for the care of modernfloors, such as vinyl flooring.

EXAMPLE 6 10 parts of 2,4-bis-(N-methyl-N-n-octadecyl-amino)-6-pyrrolidino-s-triazine were dissolved in 90 parts of isopropanol byheating to 90 on the water bath.

Leather samples were impregnated with this solution by immersion thereinfor 5 minutes, and then air-dried. The leather then contained about 13%of the aforesaid s-tri azine, calculated on the dry weight of theleather.

The impregnated leather samples were then immersed for several hours inwater together with untreated control samples of the same leather. Whileuntreated leather absorbed water very rapidly, e.g., 100% (calculated onthe weight of the dry leather) within the first hour, and a total of120% in 18 hours, the impregnated leather samples absorbed water muchmore slowly. Thus the amount of water absorbed reached 100% only after18 hours.

EXAMPLE 7.

4.480 parts ofN,N'-bis-[2-morpholino-4-N-methyl-noctadecylamino-s-triazinyl-( 6)]-piperazine,

3.3 60 parts of an isocyanate polymeric wax (softening point 93 A.N.25-35; S.N. 50-65; penetration 1-3 at 100 g. 25 5 sec.), as described inManufacturing Chemist and Aerosol News, July 1965, p. 59,

2.800 parts of montanic acid ester wax (M.P. 80-83 A.N. 20-30; S.N.135-150),

0.560 part of montanic acid ester wax (M.P. 80-83 A.N. 140-155; S.N.160-180),

0.448 part of the same emulsifier as used in Example 1,

0.560 part of aminomethyl propanol,

0.224 part of a saturated aqueous solution of KOH,

66.568 parts of water.

2.80 parts of the same colophonium-modified phenolic resin as used inExample 1, 1.00 part of concentrated ammonia, 16.20 parts of water.

0.01 part of the same wetting agent as used in Example 1, 0.99 part ofwater.

The compounds of the mixture (a), with the exception of water, aremelted at 150, the homogeneous melt is cooled to 100-110" and thenslowly added, while stirring strongly, to the boiling water. Theemulsion formed is cooled to room temperature and first the mixture (b)and then mixture (0) are added while stirring.

The resulting gloss-imparting emulsion Wax composition is excellentlysuitable for the care of modern floors. More especially the treatedfloors are rendered non-slippery. This is due to an anti-slip efiect ofthe above-described composition which is not shown in any comparabledegree by a similar composition in which, however,N,N-bis-[2-morpholino-4-N-methyl noctadecylaminos-triazinyl-(6)]-piperazine is replaced by an equal amountof the third of the above-mentioned constituents, namely montanic acidester wax of M.P. 80-83", A.N. 20-30 and SN. 135-150.

When vinyl asbestos plates are polished with the composition accordingto Example 7, on the one hand, and with the last-mentioned conventionaltriazine derivativefree composition on the other hand, and the dynamicslip resistance of the treated plates is measured, e.g. by Method No. 30of Standard Methods of Testing Paint, Varnish, Lacquer and RelatedProducts, published as DEF- 1053 by the British Ministry of Defense,then, the com- QTl 12 position according to the invention shows a valueof 9.1 lbs., while the conventional composition compared therewith showsa value of only 1.5 lbs.

If similar dynamic slip resistance values as shown by the aforesaidcomposition of Example 7 are to be attained also in the case of theconventional composition, a considerable amount of adjuvant such asfinely dispersed silica would have to be added, but would lead to astrong reduction of gloss in the polished surface. Floors treated withthe composition according to the invention therefore combine high glosswith pronounced slip-resistance.

EXAMPLE 8 4.200 parts of1,4-bis[2',4-bis-N-methyl-n-octadecylamino-s-triazinyl- (6)]-piperazine, 1.355 parts of montanic acid ester wax (M.P. -83";

A.N. 20-30; S.N. -150),

4.200 parts of the same isocyanate polymeric wax as used in Example 7,

0.735 part of montanic acid wax (M.P. 80-83"; A.N.

0.630 part of the same emulsifiying agent as used in Example 1,

0.210 part of KOH 10%, 0.630 part of aminomethyl propanol, 62.04 partsof water.

3.50 parts of the same colophonium-modified phenolic resin as used inExample 1, 1.00 part of concentrated ammonia, 20.50 parts of water.

0.10 part of a condensation product of nonylphenyl and ethylene oxide(molar ratio about 1:15), 0.90 part of water.

The components of the mixture (a), with the exception of water, aremelted at the homogeneous melt is cooled to 100-110" and then slowlyadded, while stirring strongly, to the boiling water. The emulsionformed is cooled to room temperature and first the mixture (b) and thenmixture (c) are added while stirring.

The resulting gloss-imparting emulsion wax composition is excellentlysuitable for the care of modern floors. When subjecting vinyl asbestosplates to a treatment with the composition according to Example 8 on theone hand, and with a similar composition in which the triazinederivative has been replaced by an equal amount of montanic acid esterwax (second component of the above composition) on the other hand, andtesting the slip resistance of the differently treated plates in thesame manner as described in Example 7, then a dynamic slip resistance of8.6 lbs. is found in the case of plates treated with the compositionaccording to Example 8 as compared with a value of about 1.5 lbs. in thecase of the triazine derivative-free composition.

Floors treated with the composition of Example 8 thus combine highgloss, which is even enhanced after washing with water or alkalinedetergents, with an unexpectedly high slip-resistance.

EXAMPLE 9 Similar surface-treating compositions according to theinvention are produced by replacing the triazine component in each ofthe compositions of the preceding examples by an equivalent amount of ans-triazine of the Formula I in which A, B and C represent thesubstituent grolups shown in the respective columns of the following tabe.

The s-triazine derivatives are produced by the methods exemplifiedhereinbefore using equivalent amounts of correspondingly substitutedstarting materials.

TABLE .Continued CzHAB! Cu n nHu

CaHI

I TABLE-Continued Example it t .-r t. l No.7 A B C M.P., C

N 4o -N -N N-CH; -N N- N' N-oH,

u n N sCr-N-JlmHzz N 41 N 7 -N NC:Hr -N N- N N-C H;

nHn N s 2N-.CiaHa1 CH: (5.11.015 0H;

N 42 N\ .N\ N N( 'N 1: 02 4011 N CraHu N(CH4OH)3 C4110 crHaOH C4119 N4a) N\ -N\ -N N Y1 mHn 4 u H 1 Y L; mHn

N(C4H3OH)1 C H CsHuOH a u ,N 44 N\ -N --N N( ]N\ Cia n CrHoB! N L CiaHuCompounds falling under Formula I mentioned in Examples 4, 5 and 6 areproduced analogously to the process illustrated in Examples 1, 2 and 3,from the correspondingly substituted starting materials.

We claim:

1. A compound of the formula;

methylpiperazino) 4 morpholino 6(N-methyl-N-noctadecylamino)-s-triazine.

4. A compound according to claim 1 which is 2,4-bis- (N-methyl N noctadecylamino)-6-(4'-methyl piperazino)-s-triazine.

5. A compound of the formula R1 7 B1 ,N J I 45 R: N R2 N N R2 wherein rR represents alkyl of from 1 to 5 carbon atoms; w

R represents alkyl of from 10 to 18 carbon atoms; B representspyrrolidino, morpholino, piperidino, hexamethyleneimino, or 4-(loweralkyl) -piperazmo; and

R represents alkyl of from 1 to 5 carbon atoms; R represents alkyl offrom 10 to 18 carbon atoms; and each of R and R represents alkyl of from1 to 5 car- C1 represents h f p Pe bon atoms substituted by a memberselected from R71 'the group consisting of hydroxyl, fluorine, chlorineand bromine.

\ v 6. A compound according to claim 5 which is 2,4-bis- (N-methyl N noctadecylamino)-6-[N-(}3-hydroXyin which R and R have the meaningsascribed to them above, pyrrolidino, morpholino piperidino,hexamethyleneimino, 4-(lower alkyl)v-p1peraz1no, or

the grouping ethyl) -N- (fi-chloroethyl) amino]-s-triazine.

. References Cited UNITED STATES PATENTS 3/1967 Kleemann 260-249.6

OTHER REFERENCES Smoline et al.: s-Triazines and Derivatives,Interscience-Pub. Inc;,-New York (1959), pp. 360-3.

in which each of 'R and R is alkyl of from 1 to 5 1 carbon atomssubstituted bya-member selected from the group consisting of hydroxyl,fluorine; chlorine and bromine.

2. A compound according to claim 1 which is2-rnorpholino-4,6-bis-(N-methyi N n octadecylamino)-striazine.

A compound. sst lia .t2.sla zn .i lwlaiqairkvlfi.

HENRY R. JILES, Primary Examiner I. M. FORD, Assistant Examiner US. Cl.X.R.

US 2207 DIV A/l UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONDated September 1; 197

Patent No.

Inventofl Denis Varsanvi and Willv Roth It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column 19, last line: delete "in ai iiin up NM 1 mm (SEAL) Atteat:

EdwanIM-Fletcher,1r. m E. W, J3 Atbesting Officer Masha. PatentsUSCOMM-DC 50376-P69 FORM PO-IOSO (10-69) h u s GOVERNNENY murmur; orncr:1900 O-366-3.\l

